US2701252A - Isoindolenine compounds - Google Patents
Isoindolenine compounds Download PDFInfo
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- US2701252A US2701252A US2701252DA US2701252A US 2701252 A US2701252 A US 2701252A US 2701252D A US2701252D A US 2701252DA US 2701252 A US2701252 A US 2701252A
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- US
- United States
- Prior art keywords
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- isoindolenine
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- solution
- Prior art date
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- Expired - Lifetime
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- 150000001875 compounds Chemical class 0.000 title claims description 40
- 239000000460 chlorine Substances 0.000 claims description 50
- 229910052801 chlorine Inorganic materials 0.000 claims description 42
- UHZYTMXLRWXGPK-UHFFFAOYSA-N Phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 34
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 34
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000007513 acids Chemical class 0.000 claims 4
- 150000001805 chlorine compounds Chemical class 0.000 claims 2
- 239000000047 product Substances 0.000 description 78
- XHXFXVLFKHQFAL-UHFFFAOYSA-N Phosphoryl chloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 30
- 239000000203 mixture Substances 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- 239000006227 byproduct Substances 0.000 description 24
- XKJCHHZQLQNZHY-UHFFFAOYSA-N Phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-Dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- LQNUZADURLCDLV-UHFFFAOYSA-N Nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- 230000000875 corresponding Effects 0.000 description 12
- 125000005543 phthalimide group Chemical class 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 8
- 229960000583 Acetic Acid Drugs 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- LPUUYZVKCMCHLO-UHFFFAOYSA-N 4,5,6,7-tetrachloroisoindole-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)NC(=O)C2=C1Cl LPUUYZVKCMCHLO-UHFFFAOYSA-N 0.000 description 4
- ANYWGXDASKQYAD-UHFFFAOYSA-N 5-nitroisoindole-1,3-dione Chemical compound [O-][N+](=O)C1=CC=C2C(=O)NC(=O)C2=C1 ANYWGXDASKQYAD-UHFFFAOYSA-N 0.000 description 4
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N Cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N Perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M Potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- -1 nitro- Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001376 precipitating Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- DTNSDCJFTHMDAK-UHFFFAOYSA-N 2-cyanobenzoic acid Chemical class OC(=O)C1=CC=CC=C1C#N DTNSDCJFTHMDAK-UHFFFAOYSA-N 0.000 description 2
- TZGPACAKMCUCKX-UHFFFAOYSA-N 2-hydroxyacetamide Chemical compound NC(=O)CO TZGPACAKMCUCKX-UHFFFAOYSA-N 0.000 description 2
- BONIIQYTWOPUQI-UHFFFAOYSA-N 4-nitroisoindole-1,3-dione Chemical group [O-][N+](=O)C1=CC=CC2=C1C(=O)NC2=O BONIIQYTWOPUQI-UHFFFAOYSA-N 0.000 description 2
- YTMSIVKCVBMPFF-UHFFFAOYSA-N 4-phenylisoindole-1,3-dione Chemical group O=C1NC(=O)C2=C1C=CC=C2C1=CC=CC=C1 YTMSIVKCVBMPFF-UHFFFAOYSA-N 0.000 description 2
- 241000974482 Aricia saepiolus Species 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M Copper(I) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- 229940117389 Dichlorobenzene Drugs 0.000 description 2
- 210000002969 Egg Yolk Anatomy 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N Heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- HKOOXMFOFWEVGF-UHFFFAOYSA-N Phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N Phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N Tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- NFFUISBAYGIGBS-UHFFFAOYSA-N [Cl].P(=O)(Cl)(Cl)Cl Chemical compound [Cl].P(=O)(Cl)(Cl)Cl NFFUISBAYGIGBS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing Effects 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 2
- 235000013345 egg yolk Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229940067157 phenylhydrazine Drugs 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- UKNAYQWNMMGCNX-UHFFFAOYSA-N sodium;[hydroxy(phenyl)methyl]-oxido-oxophosphanium Chemical compound [Na+].[O-][P+](=O)C(O)C1=CC=CC=C1 UKNAYQWNMMGCNX-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- 230000001131 transforming Effects 0.000 description 2
- 238000004450 types of analysis Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
Definitions
- Thepresent invention relates to new chlorine containi-ng derivatives" of isoindolenine. Furthermore the invention relates to the manufacture of isoindolenine compounds, more particularly to the manufacture of derivatives of l-arnino-3-imino-isoindolenine.
- new chlorine containing compounds are obtained by treating phthalimide or nuclear substitution products thereof, for instance halogen-, nitro-, alkylor aryl derivatives, with phosphorus pentachloride.
- phthalimides as such starting materials may be used which are converted. into phthalimide under the reaction conditions, for instance o-cyanobenzo'ic acid and its chloride.
- reaction iscarriedout by heating the reactants, preferably in a solvent indifferent to phosphorus pentachloride, such as phosphorus oxychloride, chlorobenzene or o-dichlorobenzene.
- phosphorus pentachloride such as phosphorus oxychloride, chlorobenzene or o-dichlorobenzene.
- B'oth compounds have been unknown up to the present date. They are colourless andcan be distilled in vacuo without decomposition.
- the product II boils: at l59 160" C. under 1.4- mm. pressure, the product III at 130 C. under 7 mm. pressure. Bothproducts crystallize well from cyclohexane if moisture is completely excluded.
- Product II yields long needles of M- P. 7778 C., while product III- yields coarse, fiat, rhombic crystals of the M. P. 106 -107 C.
- phthalimides for instance. nitrophthalimides, chlorine or bromine substituted phthalimides, phenyl phthalimides and alkyl substituted phthalimides.
- substituted chlorine containing isoindolenine derivatives. are obtained.
- reaction. products Apart from the aforesaid reaction products, other reaction. products the. composition of which has not been determined asyet are formedv in part as initial products and-in. part. as stable by-prod'ucts. Such by-products are described in Examples 2 and 3; they are more easily pro prised when: the reaction. isconducted at higher temperatures. No by-products are formed in the reaction of phthalimides. which are. substituted by acid radicals, for instance 4-nitroor tetrachloro phthalimide.
- the new compounds obtained. according, to the invention contain very readily exchangeable chlorine. They readily react with other compounds containing exchangeable hydrogen. or metallic atoms. and therefore may be usedfor a number of organic syntheses. Thus for instance l ,3,3-trichloro-isoindolenine yield l-amino-B-imino-isoindolenine or derivatives thereof with. ammonia or amines.
- reaction which contain more than one reactive chlorine atom, can be converted into l-amino-3-imino-isoindolenines or N-substitution products thereof with ammonia, amines or other nitrogen containing compounds like hydroxylamine, sulphonic acid amides and carboxylic acid amides.
- the reaction is preferably carried out at lower temperatures (for instance from 30 C. to +70 C.) or with cooling and in an indifferent solvent, and advantageously inthe absence of water because. of the water-sensitivity of the chlorine containing compounds.
- solvents may be used aromatic or hydroaromatic hydrocarbons or their chlorine substitution products.
- Suitable amines are primary and secondary aliphatic, cycloaliphatic and aromatic amines, for instance methylamine, ethylamine, cyclohexylamine, aniline and dimethylamine.
- the chlorine containing compounds employed as starting materials need not be isolated from their reaction solutions and purified. It is possible, however, to employ directly in the reaction the by-products liberated from the reaction of phosphorus pentachloride, for instance phosphorus oxychloride.
- Isolation of l-amino-3-imino-isoindolenines obtained according to the process of the present invention can be effected in the usual manner by filtering off after the treatment with ammonia or derivatives thereof, as' far as they precipitate from the reaction solution, or libcrating them fromthe water-soluble hydrochlorides by washing with water. They can of course also be precipitated from the reaction solutions in. form of their slightly soluble salts, for instance as nitrates.
- the derivatives of lam-ino-3-imino-isoindolenine, some of which crystallize from aqueous solutions, are valuable intermediate products in the synthesis of phthalocyanines.
- the present invention is further illustrated by the fol lowing; examples the parts being by weight:
- Example 1 A mixture of 147 parts of phthalimide and 430 parts of phosphorus pentachloride is heated under reflux to --l00" C. while stirring, with. 400- parts of o-dichlorobenzene.
- the phthalimide dissolves with a light yellow colourat'ion and evolution of HCl, within. 70-80 minutes.
- the phosphorus oxychloride produced is distilled oif under gradually decreasing pressure, and thereafter the o'dichlorobenzene at. 75 8' 5 C. under 37-17 mmt pressure whereby traces of the phosphorus pentachloride which is used in slight excess distil' over.
- a transition temperature under 17 mm.
- the distillate begins. to partially solidify in a crystalline form. After the distillate. formed in the range of 1.02"- 1146? C. which finally completely solidifies and represents about 25 parts-the major part of distillate follows at -165" C. under 17-19 mm. pressure (133 parts corresponding to 95% of theory).
- the colourless product collects partly in the liquid state and partly in the water-cooled receiver as a sublimate of coarse crystals; The distillation is complete when. the distillate turns yellow The solidification. point is about 102 C. A yellow-brown residue remains which is viscous when hot (about 57 parts).
- the same product is obtained by gradually running 11 parts of 1.3.3-trichloro-isoindolenine into excess alcoholic ammonia while the strong exothermic reaction is moderated by cooling.
- the resulting ammonium chloride preclpitates.
- a clear solution forms from which the resulting base is easily precipitated and isolated in form of slightly soluble salts by addition of dilute nitric acid, phosphoric acid, perchloric acid, or oxalic acid.
- 1-amino-3-imino-isoindolenine may also be obtained without isolation of the chlorine containing isoindolenine compounds in the following manner:
- Example 2 147 parts of phthalimide are refluxed while stirring with 208 parts of phosphorus pentachloride and 150 parts of o-dichloro-benzene. After about 20 minutes a light orange-yellow coloured solution forms at 130 C. The solution is stirred at 150 C. for a further 4 hours and the phosphorus oxychloride produced is distilled off under reflux up to an internal temperature of 205 C. and the o-dichloro-benzene is partly distilled off. Upon cooling a small quantity of a by-product crystallizes (5 parts of brownish-golden yellow needles which are soluble in concentrated sulphuric acid with an orange-red colouration).
- the by-product is clarified by filtering and the filtrate is distilled in vacuo. After removing the o-dichlorobenzene and the first runnings from 105 C. to about 143 C. (under 15 mm. pressure) about 50 parts of an almost colourles, but finally yellowish distillate are obtained. During distillation further phosphorus oxychloride goes over whereby a larger portion of the crude product decomposes with yellow-brown colouration.
- Example 3 A mixture of 1 mol of phthalimide, 2.08 mols of phosphorus pentachloride and o-dichlorobenzene, as described in example 1, is refluxed (at about 147 C.) after the reactants have completely dissolved whereby phosphorus oxychloride distils off in such a quantity that the internal temperature rises to 160 C. From about 150 C. slightly soluble, light yellow needles precipitate from the intensely yellow coloured solution; the amount of the precipitating needles increases during 3 hours subsequent heating. The mixture is then allowed to cool to 40-50 C. and filtered ofi at that temperature. The remaining loose felt of yellow needles is well washed with benzene and dried with exclusion of moisture. The yield amounts to about 20-25 parts of a by-product denoted for convenience as byproduct A. Colourless coarse crystals precipitate from the filtrate of A on cooling overnight. The yield amounts to 12-15 parts of a by-product B.
- Example 1 By vacuum distillation as indicated in Example 1 the filtrate of B yields 1.3.3-trichloroisoindolenine in a yield of 50-60% of theory.
- the by-product A which is formed at higher temperatures only, contains chlorine and phosphorus but is free from oxygen. According to mean values of several conformable analyses the bv-product A contains about 4.5% of P, 43.3% of C, 2.1% of H, 6.3% of N and (at least) 41% of Cl.
- the product dissolves in methanol with yellow colouration (with hydrolysis). The highly diluted solution shows a greenish-blue fluorescence. On heating with formamide the product changes to a full, red-orange coloured compound crystallizing from nitrobenzene in fine needles of the melting point 354 C. which dissolve in chloro-sulphonic acid with a green colouration and show both basic and acid properties. This compound is free from chlorine and phos horus. Its composition corresponds to the formula C1sH10O2N2.
- the by-product A yields a well crystallized, red saponification and transformation product (melting point 236 C.) with potassium acetate in methanol; by heating in chlorosulphonic acid it is converted into the product described in the preceding paragraph (melting point 354 C.).
- the by-product B crystallizes from chlorobenzene in colourless. coarse. bri ht rhombs of the melting point 206-207 C. This product is free from phosphorus. According to analysis and behaviour the product should be 1.1'-bis-(3.3'-dichloroisonidolenyl)-ether.
- Example 4 Into a mixture of 305 parts of phosphorus trichloride and 500 parts of phosphorus oxychloride chlorine is introduced with stirring and external cooling until the mixture is saturated and the excess chlorine is removed by means of a current of absolutely dry air. 285 parts of tetrachloro phthalimide are added in three portions with further stirring to the phosphorus pentachloride su pension formed and the mixture is heated to -115 C. under reflux. The second and third portion of the imide are introduced after the previously charged portions have dissolved. After 45 minutes the total quantity of the diFficultly soluble imide is dissolved. The reaction is complete after heating for 2 hours.
- Example 5 96 parts of 4-nitrophthalimide (melting point 199 C.) are mixed while stirring at 95-100 C. with 215 parts of phosphorus pentachloride and 300 parts of phosphorus oxychloride; a clear solution is obtained within 2-3 hours which is stirred at the same temperature for another 4 hours. Phosphorus oxychloride and subsequently the reaction product is distilled ofi in vacuo. 177 parts (corresponding to 89% of theory) of a light yellow viscous oil (constant boiling point 167l68 C. under 6 mm. pressure) are obtained. According to analysis and behaviour the oil represents an isomeric mixture of the S-nitroand 6-nitro-l.3.3-trichloro-isoindolenines. The product yields crystallized 4-nitrophthalimide by heating with methanol.
- 1-amino-3-imino-5-nitro-isoindolenine is slightly soluble only in cold water.
- the crude product becomes greenish at 200 C. and yields a blue-green melt with the evolution of gas at 223224 C.
- the product purified by way of the difficultly soluble nitrate decomposes at about 245 C.
- the slightly soluble nitrate is obtained as a weakly yellowish coloured crystalline powder which yields a brown melt on rapid heating without discolouration to green at 258-259 C. with the evolution of gas.
- Example 6 By reacting 111.5 parts of 4 phenylpthalimide with phosphorus oxychloride and 215 parts of phosphorus pentachloride in the manner described in Example 5 the reactants dissolve with evolution of hydrochloric acid. The solution is however, deep brown-yellow coloured which indicates the formation of a relatively large proportion of by-products.
- phenyl-1,3,3-trichloroisoindolenine distils over at 2l5216 C. under 7-8 mm. pressure. The yield amounts to about 54 parts. During distillation the residue shows a tendency to foam with the evolution of gas and finally decomposes.
- the distilled portion yields an almost colourless oil of the boiling point 208210 C. under 6 mm. pressure by a second vacuum distillation; according to analysis and behaviour the oil represents phenyl-l.1.3-trichloro-isoindolenine (presumably as a mix- 1-amino-3-imino-4.5.6.7-tetra-
- the product dissolves inmoderately ture of the two possible; isomers). By cooling at cyclohexane solution of this product a part crystallizes in colourless rhombs.
- the process for the production-of chlorine containing isoindolenines which comprises treating a compound selected from the group consisting of phthalimides, o-cyanobenzoic acids and the acid chlorides o-cyanobenzoic acids with phosphorus pentachloride at temperatures.frorn.80'to.180 C.
- the process for the productionoff chlorine containing isoindolenines which. comprises; treating. one: mol. of a phthalimide with substantially one mol of phosphorus pentachloride at temperatures from 80 to C.
- aromatic hydrocarbons consisting of aromatic and hydroaromatic hydrocarbons and chlorine substituted aromatic hydrocarbons.
Description
United States Patent ISOINDOLENINE COMPOUNDS I Heinrich Vollmann, Leverkusen -Wiesdorf, and Fritz Bau- No'Drawing. Application June 25', 1952, Serial N0. 295,554
Claims priority, application Germany June 28, 1951 12 Claims. (Cl. 260--325) Thepresent invention relates to new chlorine containi-ng derivatives" of isoindolenine. Furthermore the invention relates to the manufacture of isoindolenine compounds, more particularly to the manufacture of derivatives of l-arnino-3-imino-isoindolenine.
According to the invention: new chlorine containing compounds are obtained by treating phthalimide or nuclear substitution products thereof, for instance halogen-, nitro-, alkylor aryl derivatives, with phosphorus pentachloride. Instead of phthalimides as such starting materials may be used which are converted. into phthalimide under the reaction conditions, for instance o-cyanobenzo'ic acid and its chloride.
The: reaction iscarriedout by heating the reactants, preferably in a solvent indifferent to phosphorus pentachloride, such as phosphorus oxychloride, chlorobenzene or o-dichlorobenzene. By reacting 1 mol of PCls and 1 mol of dicarboxyl-ic acid imide (I), l-chlor'o-3- oxo-isoindolenine (II) is obtained as main product. 2 mols of PC15 yield 1.3.3-trichloro-isoindolenine (III):
III
B'oth compounds have been unknown up to the present date. They are colourless andcan be distilled in vacuo without decomposition. The product II boils: at l59 160" C. under 1.4- mm. pressure, the product III at 130 C. under 7 mm. pressure. Bothproducts crystallize well from cyclohexane if moisture is completely excluded. Product II yields long needles of M- P. 7778 C., while product III- yields coarse, fiat, rhombic crystals of the M. P. 106 -107 C.
It is: possible, of course, to use in the above reaction substitution products. of phthalimides; for instance. nitrophthalimides, chlorine or bromine substituted phthalimides, phenyl phthalimides and alkyl substituted phthalimides. In this case substituted chlorine containing isoindolenine derivatives. are obtained.
Apart from the aforesaid reaction products, other reaction. products the. composition of which has not been determined asyet are formedv in part as initial products and-in. part. as stable by-prod'ucts. Such by-products are described in Examples 2 and 3; they are more easily pro duced when: the reaction. isconducted at higher temperatures. No by-products are formed in the reaction of phthalimides. which are. substituted by acid radicals, for instance 4-nitroor tetrachloro phthalimide.
The new compounds obtained. according, to the invention contain very readily exchangeable chlorine. They readily react with other compounds containing exchangeable hydrogen. or metallic atoms. and therefore may be usedfor a number of organic syntheses. Thus for instance l ,3,3-trichloro-isoindolenine yield l-amino-B-imino-isoindolenine or derivatives thereof with. ammonia or amines.
The chlorine containing derivatives of isoindolenine,
which contain more than one reactive chlorine atom, can be converted into l-amino-3-imino-isoindolenines or N-substitution products thereof with ammonia, amines or other nitrogen containing compounds like hydroxylamine, sulphonic acid amides and carboxylic acid amides. The reaction is preferably carried out at lower temperatures (for instance from 30 C. to +70 C.) or with cooling and in an indifferent solvent, and advantageously inthe absence of water because. of the water-sensitivity of the chlorine containing compounds. As solvents may be used aromatic or hydroaromatic hydrocarbons or their chlorine substitution products. Suitable amines are primary and secondary aliphatic, cycloaliphatic and aromatic amines, for instance methylamine, ethylamine, cyclohexylamine, aniline and dimethylamine. The chlorine containing compounds employed as starting materials need not be isolated from their reaction solutions and purified. It is possible, however, to employ directly in the reaction the by-products liberated from the reaction of phosphorus pentachloride, for instance phosphorus oxychloride.
Isolation of l-amino-3-imino-isoindolenines obtained according to the process of the present invention can be effected in the usual manner by filtering off after the treatment with ammonia or derivatives thereof, as' far as they precipitate from the reaction solution, or libcrating them fromthe water-soluble hydrochlorides by washing with water. They can of course also be precipitated from the reaction solutions in. form of their slightly soluble salts, for instance as nitrates. The derivatives of lam-ino-3-imino-isoindolenine, some of which crystallize from aqueous solutions, are valuable intermediate products in the synthesis of phthalocyanines.
The present invention is further illustrated by the fol lowing; examples the parts being by weight:
Example 1 A mixture of 147 parts of phthalimide and 430 parts of phosphorus pentachloride is heated under reflux to --l00" C. while stirring, with. 400- parts of o-dichlorobenzene. The phthalimide dissolves with a light yellow colourat'ion and evolution of HCl, within. 70-80 minutes. After stirring the solution at about C. for another 4 hours the phosphorus oxychloride produced is distilled oif under gradually decreasing pressure, and thereafter the o'dichlorobenzene at. 75 8' 5 C. under 37-17 mmt pressure whereby traces of the phosphorus pentachloride which is used in slight excess distil' over. At. a transition temperature (under 17 mm. pressure) of 102 C., the distillate begins. to partially solidify in a crystalline form. After the distillate. formed in the range of 1.02"- 1146? C. which finally completely solidifies and represents about 25 parts-the major part of distillate follows at -165" C. under 17-19 mm. pressure (133 parts corresponding to 95% of theory). The colourless product collects partly in the liquid state and partly in the water-cooled receiver as a sublimate of coarse crystals; The distillation is complete when. the distillate turns yellow The solidification. point is about 102 C. A yellow-brown residue remains which is viscous when hot (about 57 parts).
Upon redistillation. of the reaction product in vacuo it becomes completely colourless and is obtained almost pure. The product which boils at 157-158 C. under 19 mm. pressure crystallizes from cyclohexane, with absolute exclusion. of moisture, in colourless, coarse prismatic or rhombic crystals of the melting point 106- 107 C. The product is free from phosphorus. Ac.- cording to the mode of production: and chemical behaviour as well as to elementaryanalyses' the reaction prolcllgct' represents l.3.3-trichloro-isoindoleuine (Formula Phthalimide is obtaine'd' from the reaction product III with evolution of HCl on adding water, or by heating with methanol, ethanol and acetic acid. The reaction with ammonia leads to l-a-m-ino-3-imino-isoindolenine in an almost quantitative yield. Further definite reaction products are obtained with primary and secondary amines, even. with pyridine.
By adding dry ammonia gas to the solution of 11 parts of 1.3.3-trichloro-isoindolenine in 80 parts of benzene while cooling at 20-50 C. and stirring the solution until the ammonia gas is present in excess a colourless crystal paste is formed which contains apart from benzene which may be separated by evaporating or filtering, and ammonium chloride, 1-amino-3-imino-isoindolenine which crystallizes in part from the aqueous solution in colourless needles. By adding ammonium nitrate to the solution of the base in dilute acetic acid the latter is isolated in form of a colourless nitrate which is very dlfficultly soluble in water and methanol. The yield of dry nitrate amounts to about 8.9 parts corresponding to 83% of theory.
The same product is obtained by gradually running 11 parts of 1.3.3-trichloro-isoindolenine into excess alcoholic ammonia while the strong exothermic reaction is moderated by cooling. The resulting ammonium chloride preclpitates. By diluting with water a clear solution forms from which the resulting base is easily precipitated and isolated in form of slightly soluble salts by addition of dilute nitric acid, phosphoric acid, perchloric acid, or oxalic acid. By gradually introducing 11 parts of 1.3.3-trichloroisolndolenine into a solution of 23 parts of aniline in 100 parts of methanol a strongly exothermic reaction takes place and an intensely yellow coloured solution is formed from which the slightly water-soluble, egg-yolk hydrochloride of 1-phenylamino-3-phenylimino-isoindolenine precipitates by diluting the solution with hydrochloric acid (10%). The yield of the reaction product which can be easily isolated by filtering amounts to 16.3 parts corresponding to 98% of theory after drying in vacuo.
1-amino-3-imino-isoindolenine may also be obtained without isolation of the chlorine containing isoindolenine compounds in the following manner:
The crude 1.3.3-trichloro-isoindolenine obtained by reacting phthalimide and 2 mols of phosphorus pentachloride at a temperature substantially not exceeding 100 C. and liberated from phosphorus oxychloride formed by vacuum distillation, is dissolved in benzene and reacted with ammonia as described above.
After filtering off the resulting reaction product, drying and stirring with a little water and filtering once more a residue consisting substantially of l-amino-3-iminoisoindolenine is obtained. Apart from the free base the residue contains the chloride of the base and phosphate. The product yields copper phthalocyanine by heating with copper acetate in a mixture of glycol and formamide.
Example 2 147 parts of phthalimide are refluxed while stirring with 208 parts of phosphorus pentachloride and 150 parts of o-dichloro-benzene. After about 20 minutes a light orange-yellow coloured solution forms at 130 C. The solution is stirred at 150 C. for a further 4 hours and the phosphorus oxychloride produced is distilled off under reflux up to an internal temperature of 205 C. and the o-dichloro-benzene is partly distilled off. Upon cooling a small quantity of a by-product crystallizes (5 parts of brownish-golden yellow needles which are soluble in concentrated sulphuric acid with an orange-red colouration). The by-product is clarified by filtering and the filtrate is distilled in vacuo. After removing the o-dichlorobenzene and the first runnings from 105 C. to about 143 C. (under 15 mm. pressure) about 50 parts of an almost colourles, but finally yellowish distillate are obtained. During distillation further phosphorus oxychloride goes over whereby a larger portion of the crude product decomposes with yellow-brown colouration.
By distilling the distillate once more a colourless product (B. l 159-160 C. under 15 mm. pressure) is obtained which solidifies at 70-73 C. in fine crystals. The product crystallizes from completely dry cyclohexane in long, bright needles having a sharp melting point (7778 C.). By exposing to moist air and heating with methanol the product quickly changes to phthalimide. According to analysis and chemical behaviour the reaction product represents 1-chloro-3-oxo-isoindolenine (Formula II).
Analysis-Calculated for C8H4ONC1I C. 58.0%: H, 2.4%: N. 8.64%: Cl. 21.4%. Found: C, 58.5%; H, 2.7%; N, 8.28%; Cl, 20.8%.
Example 3 A mixture of 1 mol of phthalimide, 2.08 mols of phosphorus pentachloride and o-dichlorobenzene, as described in example 1, is refluxed (at about 147 C.) after the reactants have completely dissolved whereby phosphorus oxychloride distils off in such a quantity that the internal temperature rises to 160 C. From about 150 C. slightly soluble, light yellow needles precipitate from the intensely yellow coloured solution; the amount of the precipitating needles increases during 3 hours subsequent heating. The mixture is then allowed to cool to 40-50 C. and filtered ofi at that temperature. The remaining loose felt of yellow needles is well washed with benzene and dried with exclusion of moisture. The yield amounts to about 20-25 parts of a by-product denoted for convenience as byproduct A. Colourless coarse crystals precipitate from the filtrate of A on cooling overnight. The yield amounts to 12-15 parts of a by-product B.
By vacuum distillation as indicated in Example 1 the filtrate of B yields 1.3.3-trichloroisoindolenine in a yield of 50-60% of theory. The by-product A which is formed at higher temperatures only, contains chlorine and phosphorus but is free from oxygen. According to mean values of several conformable analyses the bv-product A contains about 4.5% of P, 43.3% of C, 2.1% of H, 6.3% of N and (at least) 41% of Cl. The product dissolves in methanol with yellow colouration (with hydrolysis). The highly diluted solution shows a greenish-blue fluorescence. On heating with formamide the product changes to a full, red-orange coloured compound crystallizing from nitrobenzene in fine needles of the melting point 354 C. which dissolve in chloro-sulphonic acid with a green colouration and show both basic and acid properties. This compound is free from chlorine and phos horus. Its composition corresponds to the formula C1sH10O2N2.
The by-product A yields a well crystallized, red saponification and transformation product (melting point 236 C.) with potassium acetate in methanol; by heating in chlorosulphonic acid it is converted into the product described in the preceding paragraph (melting point 354 C.).
The by-product B crystallizes from chlorobenzene in colourless. coarse. bri ht rhombs of the melting point 206-207 C. This product is free from phosphorus. According to analysis and behaviour the product should be 1.1'-bis-(3.3'-dichloroisonidolenyl)-ether.
Example 4 Into a mixture of 305 parts of phosphorus trichloride and 500 parts of phosphorus oxychloride chlorine is introduced with stirring and external cooling until the mixture is saturated and the excess chlorine is removed by means of a current of absolutely dry air. 285 parts of tetrachloro phthalimide are added in three portions with further stirring to the phosphorus pentachloride su pension formed and the mixture is heated to -115 C. under reflux. The second and third portion of the imide are introduced after the previously charged portions have dissolved. After 45 minutes the total quantity of the diFficultly soluble imide is dissolved. The reaction is complete after heating for 2 hours. By cooling the solution which is not discoloured a substantial part of he tachlorois in dolenine crystallizes in pure form. It is preferable to distil first the phosphorus oxychloride and thereafter the heptachloroisoindolenine in vacuo. This product distils ver at 208 C. under 6 mm. pressure. The distillate solidifies colourless in a crystalline form. The yield amounts to 35 8 parts corresponding to 84% of theory. Bv recrystallizing from completely dry benzene coarse. bri ht rhombs are obtained which become dull on drying in the vacuum desiccator with a sli ht fiow of dry air. The product melts at 167-168 C. According to the mode of manufacture, analysis and chemical behaviour the reaction product represents 1.3.3.4.5.6.7-heotachloroisoindolenine.
71.7 parts of distilled 1.3.3.4.5.6.7-heptachloroisoindolenine (B. P 208 C. under 6 mm. pressure) are dissolved in 1200 parts of dry benzene and the solution is stirred with ammonia gas while cooling at 2030 C. A thick precipitate forms which is yellowi h at the beginning and becomes colourless afterwards. When the adsorption of ammonia ceases the mixture is filtered by suction, the adhering benzene is separated by drying and the crude product is mixed while stirring with about 1000 parts of water, filtered off and washed with cold water to remove the ammonium chloride. The colourless to light grey residue is dried at vacuo up to 35 C. The yield of l-amino- 3-imino-4.5.6.7-tetrachloroisoindolenine is almost quantitative. The product becomes greenish by heating above 260 C. and melts at 295300 C. with the evolution of gas. By heating the product to the boil in nitrobenzene in soluble, clear green perchloro-copper-phthalocyanine forms in a good yield. chloro-isoindolenine is insoluble in water, pyridine, methanol and other low boiling solvents. Conversion of the product takes place in high boiling media such as nitrobenzene; glycol or tetrahydro-naphthalene, while ammonia is split ofi. heated acetic anhydride from which an acetyl derivative crystallizes on cooling.
By adding excess aniline in drops to a benzene solution of 1.3.3.4.5.6.7-heptachloro-isoindolenine an intensely yellow coloured product precipitates. After shortly heating on the water-bath the mixture is cooled under reflux, filtered and the resultinganiline hydrochloride. is washed with methanol. The residual. 1-phenylamino-3-phenylimino-4.5.6.7tetrachloro-isoindolenine is obtained in a completely pure state. It crystallizes from chlorobenzene in yellow needles of the M. P. 243244 C., dissolves in concentrated sulphuric acid with a pure yellow colouration and forms a red-orange coloured, slightly soluble salt with concentrated hydrochloric acid.
Example 5 96 parts of 4-nitrophthalimide (melting point 199 C.) are mixed while stirring at 95-100 C. with 215 parts of phosphorus pentachloride and 300 parts of phosphorus oxychloride; a clear solution is obtained within 2-3 hours which is stirred at the same temperature for another 4 hours. Phosphorus oxychloride and subsequently the reaction product is distilled ofi in vacuo. 177 parts (corresponding to 89% of theory) of a light yellow viscous oil (constant boiling point 167l68 C. under 6 mm. pressure) are obtained. According to analysis and behaviour the oil represents an isomeric mixture of the S-nitroand 6-nitro-l.3.3-trichloro-isoindolenines. The product yields crystallized 4-nitrophthalimide by heating with methanol.
By reacting 264 parts of nitro-1.3.3-trichloro-isoiudolenine in benzene with ammonia in analogous manner as described in Example 4, 215 parts (corresponding to 97% of theory) of chlorine-free 1-amino-3-imino-5-nitro-isoindolenine is obtained in form of a faintly yellowish powder. By heating the product with the calculated amount of copper-(I)-bromide in pyridine the known tetranitro-copper-phthalocyanine is obtained.
1-amino-3-imino-5-nitro-isoindolenine is slightly soluble only in cold water. The crude product becomes greenish at 200 C. and yields a blue-green melt with the evolution of gas at 223224 C. The product purified by way of the difficultly soluble nitrate decomposes at about 245 C. By dissolving the nitro compound in a mixture of methanol and glacial acetic acid and precipitating after filtering with ammonium nitrate the slightly soluble nitrate is obtained as a weakly yellowish coloured crystalline powder which yields a brown melt on rapid heating without discolouration to green at 258-259 C. with the evolution of gas.
The product obtained by heating 1-arnino-3-imino-nitroisoindolenine with 2 mols of phenylhydrazine in glacial acetic acid yields an orange-yellow methanol solution which turns clear red-violet in the air after addition of sodium hydroxide solution.
By adding hydrosulfite to a cold aqueous alkaline suspension of 1-amino-3-imino-5-nitroisoindolenine the intensely yellow coloured, very easily water-soluble 1.5- diamino-3-imino-isoindolenine is obtained.
Example 6 By reacting 111.5 parts of 4 phenylpthalimide with phosphorus oxychloride and 215 parts of phosphorus pentachloride in the manner described in Example 5 the reactants dissolve with evolution of hydrochloric acid. The solution is however, deep brown-yellow coloured which indicates the formation of a relatively large proportion of by-products. By carefully distilling the crude product remaining after distilling off phosphorus oxychloride, phenyl-1,3,3-trichloroisoindolenine distils over at 2l5216 C. under 7-8 mm. pressure. The yield amounts to about 54 parts. During distillation the residue shows a tendency to foam with the evolution of gas and finally decomposes. The distilled portion yields an almost colourless oil of the boiling point 208210 C. under 6 mm. pressure by a second vacuum distillation; according to analysis and behaviour the oil represents phenyl-l.1.3-trichloro-isoindolenine (presumably as a mix- 1-amino-3-imino-4.5.6.7-tetra- The product dissolves inmoderately ture of the two possible; isomers). By cooling at cyclohexane solution of this product a part crystallizes in colourless rhombs.
We claim:
1. The process for the production-of chlorine containing isoindolenines which comprises treating a compound selected from the group consisting of phthalimides, o-cyanobenzoic acids and the acid chlorides o-cyanobenzoic acids with phosphorus pentachloride at temperatures.frorn.80'to.180 C.
2. The process for the productionoff chlorine containing isoindolenines which. comprises; treating. one: mol. of a phthalimide with substantially one mol of phosphorus pentachloride at temperatures from 80 to C.
3. The process for the production of chlorine containing isoindolenines which comprises treating one mol of a phthalimide with two' to three mols of phosphorus pentachloride at temperatures from 80 to 180 C.
4. The process for the production: of chlorine containing isoindolenines which comprises treating phthalirnides with phosphoruspentachlorid'ein a solvent; indifferent to phosphorus pentachloride, said solvent being selected from the group consisting of phosphorus oxychloride, chlorobenzene and o-dichloro-benzene at temperatures from 80 to 180 C.
5. As new compounds chlorine containing isoindolenines of the general formula wherein M stands for a substituent selected from the group consisting of O and C12, X stands for a substituent selected from the group consisting of H, N02, Cl, and CsHa, and It stands for an integer from 1 to 4.
6. As new compound 8. As new compounds 9. As new compound C1 C1 C1 7 10. As new compounds l OQHI N 11. The process for the production of 1-amino-3-iminoisoindolenine derivatives which comprises treating 1.3.3- trichloro-isoindolenines with a compound of the general formula:
12. The process for the production of 1-amino-3- imino-isoindolenine derivatives which comprises treating 1.3.3-trichloro-isoindolenines with a compound of the general formula:
consisting of aromatic and hydroaromatic hydrocarbons and chlorine substituted aromatic hydrocarbons.
References Cited in the file of this patent Berichte, vol. 12, pp. 456-461. Beilstein: Handbuch der Organischen Chemie, vol. 21, page 287, citing Le Royer, Annalen, vol. 238, page 356.
Claims (1)
1. THE PROCESS FOR THE PRODUCTION OF CHLORINE CONTAINING ISOINDOLENINES WHICH COMPRISES TREATING A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PHTHALIMIDES, O-CYANOBENZOIC ACIDS AND THE ACID CHLORIDES O-CYANOBENZOIC ACIDS WITH PHOSPHORUS PENTACHLORIDE AT TEMPERATURES FROM 80 TO 180*C.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2964533A (en) * | 1957-12-19 | 1960-12-13 | Geigy Ag J R | Heterocyclic compounds and process for the production thereof |
US2973369A (en) * | 1961-02-28 | J-dichloro-isoindolinones | ||
US2973358A (en) * | 1956-07-13 | 1961-02-28 | Geigy Ag J R | 4, 5, 6, 7-tetrachloro-3-imino-isoindoline-1-one derivatives |
US2980691A (en) * | 1954-07-20 | 1961-04-18 | Du Pont | Halogenated metal-phthalocyanine precursors |
US3123461A (en) * | 1964-03-03 | Herbicidal compositions | ||
US4061654A (en) * | 1971-07-02 | 1977-12-06 | Polaroid Corporation | Novel tetrazaporphins |
-
0
- US US2701252D patent/US2701252A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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None * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2973369A (en) * | 1961-02-28 | J-dichloro-isoindolinones | ||
US3123461A (en) * | 1964-03-03 | Herbicidal compositions | ||
US2980691A (en) * | 1954-07-20 | 1961-04-18 | Du Pont | Halogenated metal-phthalocyanine precursors |
US2973358A (en) * | 1956-07-13 | 1961-02-28 | Geigy Ag J R | 4, 5, 6, 7-tetrachloro-3-imino-isoindoline-1-one derivatives |
US3076815A (en) * | 1956-07-13 | 1963-02-05 | Geigy Ag J R | 3-imido-isoindolinones |
US2964533A (en) * | 1957-12-19 | 1960-12-13 | Geigy Ag J R | Heterocyclic compounds and process for the production thereof |
US4061654A (en) * | 1971-07-02 | 1977-12-06 | Polaroid Corporation | Novel tetrazaporphins |
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